US4510042A - Heavy oil process with hydrovisbreaking, hydrodemetallation and hydrodesulfuration - Google Patents

Heavy oil process with hydrovisbreaking, hydrodemetallation and hydrodesulfuration Download PDF

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US4510042A
US4510042A US06/567,208 US56720883A US4510042A US 4510042 A US4510042 A US 4510042A US 56720883 A US56720883 A US 56720883A US 4510042 A US4510042 A US 4510042A
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catalyst
process according
alumina
charge
pore volume
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Alain Billon
Yves Jacquin
Jean-Pierre Peries
Herve Toulhoat
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IFP Energies Nouvelles IFPEN
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/883—Molybdenum and nickel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/107—Atmospheric residues having a boiling point of at least about 538 °C

Definitions

  • This invention relates to the treatment of heavy oils or heavy oil fractions of high asphaltene content, in order to convert them to lighter fractions whose transport and treatment by usual refining processes is easier. Oils from coal hydrogenation may also be treated.
  • the invention solves the problem of converting a viscous, non transportable, crude oil of high metals, sulfur and asphaltenes content and comprising more than 50% of constituents having a normal boiling point higher than 520° C., to a stable, easily transportable hydrocarbon product, of low metals, sulfur and asphaltenes contents and having only a reduced content, for example less than 20% by weight, of constituents of normal boiling point higher than 520° C.
  • Boscan or Cerro Negro crude oil may contain from 200 to 1000 ppm by weight or more of metals; these metals are mainly vanadium and nickel, together with variable proportions of iron and other metals.
  • hydrotreatment catalyst may be used over several weeks or several months without deactivation.
  • the process of the invention comprises the essential following steps:
  • FIG. 1 is a plot of the pore distribution of a catalyst (A) suitable for use in step (B) of the process of the invention, and of a bimodal (B) or monomodal (C) prior art catalyst.
  • FIGS. 2-6 show electron micrographs of catalyst A, at various magnifications.
  • FIGS. 7-10 show electron micrographs of catalyst B.
  • FIG. 11 is a schematic flow diagram for a process according to the invention.
  • step (c) is conducted in two successive stages:
  • the ratio by weight of catalyst C 2 to catalyst C 1 is preferably from 1:1 to 9:1.
  • step (b) The catalyst of step (b) has been described in allowed U.S. patent application Ser. No. 505,557 filed June 17, 1983 whose disclosure is herein incorporated by way of reference.
  • the essential information is summarized below:
  • a large proportion, mostly at least 50%, of the acicular plates have a size along their longer axis from 0.05 to 5 micrometers and preferably from 0.1 to 2 micrometers, a ratio of said size to their average width from 2 to 20 and preferably from 5 to 15, a ratio of said size to their average thickness from 1 to 5000 and preferably from 10 to 200.
  • a large proportion, often at least 50% of the acicular plates conglomerates form a collection of pseudo-spherical particles of an average size from 1 to 20 micrometers, preferably from 2 to 10 micrometers.
  • Such a structure is very adequately represented, for example, by pictures of a heap of thorny chesnut-hulls or a heap of sea-urchins.
  • FIG. 1 comparatively shows the pore distribution curve of a catalyst (A) as used in step (b) of the invention and those corresponding to monomodal (C) or bimodal (B) catalysts of the prior art.
  • the catalyst use in the process of the invention has preferably the following pore distribution:
  • total pore volume 0.7 to 2.0 cc/g, preferably 0.90 to 1.30 cc/g.
  • % of the total volume in pores of average diameter smaller than 10 nanometers 0-10.
  • % of the total pore volume in pores of average diameter from 500 to 1000 nanometers 5-50.
  • % of the total pore volume in pores of average diameter larger than 1000 nanometers 5-20.
  • the specific surface of this catalyst is from 50 to 250 m 2 /g and more preferably from 120 to 180 m 2 /g.
  • FIGS. 2 to 5 show four microphotographs with enlargements of 300 times, 3000 times, 10,000 times and 20,000 times respectively, of a catalyst according to the invention (catalyst A), well illustrating the particular structure similar to juxtaposed sea-urchins as mentioned above.
  • FIG. 6 shows a microphotograph, with a nominal enlargement of 110,000 times, of an acicular plates beam of catalyst A, illustrating the typical shape of these plates.
  • the intervals between the opposite arrows with reference number 1 identify the edgewise plates trace and are an approximate measure of the thickness of these plates.
  • the interval between the opposite arrows indicated with reference 2 identifies a plate parallel to the plane of the photograph and is a measure of the average width of said plate.
  • the scale is 9 nanometers per millimeter and the dark-colored portions correspond to the catalytic substance.
  • FIGS. 7 to 10 show four microphotographs taken with the same respective enlargements as in FIGS. 2 to 5 and with the same apparatus, of a catalyst sample (catalyst B) prepared by using bimodal alumina balls obtained by the process patented in France under No. 2 449 474: these photographs are a good illustration of the description given in the latter patent, i.e. that macroporosity results from interparticle voids existing between spheroidal microporous particles whose granulometry distribution and piling compactness determine the macroporous volume and the macropores size.
  • the dark-colored areas correspond to void spaces in the catalyst structures, i.e.
  • the distribution of the macropores diameters of catalyst B may be measured on the photographs and effectively corresponds to that measured by means of a mercury-pump porosimeter, as shown in FIG. 1.
  • the comparison of the microphotographs makes apparent that the microporous spheroidal particles of catalyst B do not have the sea-urchin structure as obtained for catalyst A used in the step (a) of the invention.
  • step (b) of the present process have an excellent resistance to clogging of the pore openings; this result may be explained as follows:
  • the pores of these catalysts formed in major part of void spaces located between the radially oriented acicular plates, are "wedge" pores, hence, of continuously varying diameter.
  • these radially oriented pores are not necessarily linear.
  • these radially oriented pores are not channels giving access to micropores of diameters lower than 10 nanometers, as in the known catalysts, but they form themselves a mesoporosity resulting in a catalytically active surface.
  • a catalyst for use in step (b) of the invention may be prepared according to the following method, without limiting the invention to this particular method of preparation:
  • Conglomerates of alumina particles of a size from about 0.1 to 10 millimeters or of alumina powder particles of a size from about 20 to 100 micrometers having themselves the above-mentioned sea-urchins structure and having substantially the same characteristics as those of the catalyst of the invention, particularly as concerns the shape and the size of the plates and conglomerates, the specific surface and the porosity, are used as carrier.
  • catalytic metals i.e. at least one metal or compound of a metal pertaining at least to one of groups V, VI and VIII (iron group) of the periodic classification, more particularly one or more of the following metals: molybdenum, tungsten, iron, vanadium, cobalt and nickel.
  • Preferred associations thereof are molybdenum+cobalt, molybdenum+nickel, vanadium+nickel, tungsten+nickel.
  • the above-mentioned metals are mostly introduced as precursors such as oxides, acids, salts, organic complexes, in such amounts that the catalyst contains from 0.5 to 40% and preferably from 1 to 20% by weight of these metals, as oxides. These precursors are well known and hence need not be listed here.
  • the final step comprises an optional drying and a thermal treatment at a temperature from 400° to 800° C.
  • the alumina conglomerates may be manufactured from alumina, optionally containing other elements, for example sodium, rare earths or silica.
  • Alumina containing from 100 to 1000 ppm by weight of silica is preferred. The operation is preferably conducted as follows:
  • Aluminum conglomerates are treated in an aqueous medium formed of a mixture of at least one acid able to dissolve at least a portion of the alumina conglomerates and at least one compound supplying an anion capable to combine with the dissolved aluminum ions, this latter compound being a chemical compound different from the above-mentioned acid.
  • the resultant conglomerates are simultaneously or subsequently subjected to a treatment at a temperature from about 80° C. to about 250° C. for a period from about a few minutes to about 36 hours.
  • the conglomerates are optionally dried and are subjected to thermal activation at a temperature from about 500° C. to about 1100° C.
  • the active alumina conglomerates according to the invention may be prepared from an active alumina powder of insufficiently crystallized and/or amorphous structure, for example one obtained according to the process disclosed in the French Pat. No. 1,438,497.
  • the active alumina is generally obtained by quick dehydration of aluminum hydroxides such as bayerite, hydrargillite or gibbsite, nordstrandite or aluminum oxyhydroxides such as boehmite and diaspore.
  • the active alumina agglomeration is achieved by methods well known in the art and particularly by pelletizing, extrusion, shaping as balls in a revolving bowl granulator, etc.
  • this agglomeration is effected, as it is well known in the art, with addition of porogenous agents to the mixture to be agglomerated.
  • the porogenous agents are mainly wood dust, charcoal, cellulose, starch, naphthalene, and more generally any organic compound liable to be removed by calcination.
  • the conglomerates are then optionally subjected to maturation, drying and/or calcination.
  • the resultant active alumina conglomerates have the following characteristics: their loss on heating, measured by calcination at 1000° C., is from about 1 to about 15%, their specific surface is from about 100 to about 350 m 2 /g and their total pore volume is from about 0.45 to about 1.5 cc/g.
  • the active alumina conglomerates are then treated in an aqueous medium consisting of a mixture of at least one acid for dissolving at least a portion of the alumina conglomerates and at least one compound supplying an anion capable to combine with the dissolved aluminum ions.
  • an acid able to dissolve at least a portion of the alumina conglomerates is any acid which, when contacted with the active alumina conglomerates as above defined, dissolves at least a portion of the aluminum ions.
  • the acid must dissolve at least 0.5% and at most 15% by weight of the alumina of the conglomerates. Its concentration in the aqueous treatment medium must be lower than 20% by weight and preferably from 1% to 15%.
  • Strong acids such as nitric acid, hydrochloric acid, perchloric acid, sulfuric acid or weak acids at a concentration sufficient to provide a pH lower than about 4, are preferably used.
  • a compound supplying an anion able to combine with dissolved aluminum ions is any compound able to liberate in solution an anion A(-n) liable to form with cations Al(3+), products having an atomic ratio n(A/Al) lower than or equal to 3.
  • An illustration of particular compounds is given by basic salts of general formula Al 2 (OH) ⁇ Ay wherein O ⁇ 6; ny ⁇ 6; n representing the number of charges of anion A.
  • the concentration of this compound in the aqueous treatment medium must be lower than 50% by weight and preferably from 3% to 30%.
  • Preferred compounds are those able to liberate in solution anions selected from the group consisting of the nitrate, chloride, sulfate, perchlorate, chloroacetate, dichloroacetate, trichloroacetate, bromoacetate, and dibromoacetate anions and the anions of the general formula: ##STR1## wherein R is a radical selected from the group comprising H, CH 3 , C 2 H 5 , CH 3 CH 2 CH 2 , (CH 3 ) 2 CH.
  • the compounds able to liberate in solution the anion A(-n) may effect this liberation, either directly, for example by dissociation or indirectly, for example by hydrolysis.
  • the compounds may in particular be selected from the group comprising: inorganic or organic acids, anhydrides, organic or inorganic salts, esters.
  • inorganic salts there can be mentioned the alkali or alkaline-earth metals salts soluble in aqueous medium such as the sodium, potassium, magnesium, calcium, and ammonium salts, the aluminum salts and the rare earth metal salts.
  • This treatment may be effected either by dry impregnation of the conglomerates or by immersion of the conglomerates in an aqueous solution of the above-mentioned mixture of acid with the compound supplying the desired anion.
  • Dry impregnation means contacting the alumina conglomerates with a volume of solution smaller than or equal to the total pore volume of the conglomerates.
  • mixtures of nitric and acetic acids or of nitric and formic acids are used as aqueous medium.
  • the resultant conglomerates are simultaneously or successively subjected to a treatment at a temperature from about 80° to about 250° C. for about 5 minutes to about 36 hours.
  • This hydrothermal treatment does not result in any alumina loss.
  • the operation is preferably conducted at a temperature from 120° to 220° C., for 15 minutes to 18 hours.
  • This treatment constitutes a hydrothermal treatment of the active alumina conglomerates which results in conversion of at least a portion thereof to boehmite.
  • This hydrothermal treatment may be effected either under saturating vapor pressure or under a pressure amounting to at least 70% of the saturating vapor pressure corresponding to the treatment temperature.
  • the concentration of acid and of compound in the treatment mixture and the hydrothermal treatment conditions are such that no alumina loss occurs.
  • the porosity increase after the treatment is hence due to the expansion of the conglomerates during the treatment and not to an alumina loss.
  • the resultant conglomerates are then optionally dried at a temperature generally from about 100° to 200° C. for a sufficient time to remove chemically uncombined water.
  • the conglomerates are then subjected to thermal activation at a temperature from about 500° C. to about 1100° C. for a period from about 15 minutes to 24 hours.
  • the activation operations may be performed in several steps. Preferably the activation is performed at a temperature from about 550° C. to 950° C.
  • a packed filling density from about 0.36 to 0.75 g/cm 3 .
  • a total pore volume (T P V) from 0.7 to about 2.0 cm 3 /g.
  • a specific surface measured by the B.E.T method from about 80 to about 250 m 2 /g.
  • a mechanical strength from 2 to about 20 kg, measured by the grain-to-grain crushing method.
  • the above-mentioned process for manufacturing alumina conglomerates results in particular in a completely unexpected modification in the distribution of the pore volumes in accordance with the pores sizes of the untreated conglomerates. It makes possible in particular to increase the proportion of pores of a size from 10 to 100 nanometers, to reduce the proportion of pores of a size lower than 10 nanometers and to decrease the proportion of pores of a size greater than 500 nanometers while not substantially modifying the proportion of the pores of a size from 100 to 500 nanometers.
  • the resultant alumina conglomerates are optionally thermally stabilized by rare earth metals, silica or alkaline-earth metals.
  • Step (c) of the process, as specified above, is preferably conducted with the use of two successive catalyst beds, referred to as (C 1 ) and (C 2 ).
  • the carrier of catalyst (C 1 ) preferably consists of low-acidity alumina, i.e. having a neutralization heat by ammonia adsorption at 320° C. lower than 40 joules (and preferably lower than 30 joules) per gram of alumina under an ammonia pressure of 0.4 bars.
  • This alumina carrier has a surface from 50 to 300 m 2 /g and preferably from 40 to 150 m 2 /g and a pore volume generally from 0.4 to 1.3 cm 3 /g.
  • An example of a carrier of this type is alumina subjected to autoclaving under steam pressure.
  • Catalyst (C 2 ), used in the second catalyst bed, will be preferably incorporated with a carrier of greater acidity than catalyst carrier (C 1 ): its acidity, determined as above by ammonia adsorption, will be preferably higher than 30 joules/g. Its surface is preferably from 150 to 350 m 2 /g and its pore volume preferably from 0.4 to 1 cm 3 /g.
  • carriers having these characteristcs are ⁇ -alumina (e.g. boehmite) or ⁇ -alumina (e.g. bayerite) or carriers of the alumina/magnesia or silica/magnesia type containing about 5 to 10% by weight of magnesia.
  • active metals e.g. Mo, W, Ni, Co, Fe
  • steps (b) and (c) of the process are conventional. These catalysts operate mainly in their sulfurized form; their sulfuration may be effected before the treatment of the charge or may result by contact with the feed in situ.
  • Step (a) is conducted in the presence of hydrogen in a reaction space either void or containing a relatively inert material, at a temperature from 420° to 500° C., under a pressure from 40 to 200 bars, the residence time of the charge being about 10s to 15 minutes and the hydrogen proportion usually from 300 to 3000 Nm 3 /m 3 .
  • Step (b) is conducted at a temperature generally from 350° to 425° C., under a pressure from 40 to 200 bars, at a hourly flow rate of the liquid charge from 0.2 to 2 m 3 /m 3 /h, the hydrogen proportion being usually from 300 to 3000 Nm 3 /m 3 .
  • Step (c) is conducted at 300° to 425° C., under the pressure from 30 to 200 bars, the hydrogen proportion being usually from 500 to 3000 Nm 3 /m 3 and the liquid charge hourly feed rate from 0.2 to 2 m 3 /m 3 /h.
  • FIG. 11 The process of the invention is illustrated by FIG. 11.
  • a mixture of asphaltic heavy oil with hydrogen is fed through line 1 to a hydrovisbreaking furnace 2, then through line 3 to the catalytic hydrodemetallation reactor 4.
  • the effluent is fed through line 5 to reactor 6 containing a first catalyst bed 7 and a second catalyst bed 8.
  • the final product is withdrawn from line 9.
  • the flow of the reactants may be directed upwardly in one of reactors 4 and 6 or in both of them.
  • the catalysts may be in fixed, moving or expanded bed. Additional hydrogen may be supplied between the reactors. It may be considered, although it is less desirable, to fractionate the effluent products from reactors 2 and/or 4, so as to supply only a portion of these products to the next reactor (4 and/or 6).
  • the final distillation of the products obtained by the process is not shown; it is usually unnecessary or may be effected at the delivery point of the hydrocarbon oil when the latter is supplied, through line 9, to a pipe line, a transport ship or other transportation means.
  • the charges which may be treated according to the invention are, for example, crude oils, vacuum residues, straight-run residues, oils from bituminous shales or sands, asphalts or oils from coal liquefaction.
  • a Cerro Negro crude oil is treated, whose characteristics are as follows:
  • Ni+V 500 ppm by weight.
  • Asphaltenes (extracted with heptane) 10.5% by weight.
  • Viscosity 249 cSt (249 mm 2 /s) at 100° C.
  • the effluent is passed, with additional hydrogen, over a catalyst (A) containing, by weight:
  • FIGS. 2 to 5 show microphotographs of catalyst A taken with a scanning electron microscope of trade mark JEOL, Model JSP 35 CF, with respective enlargements of 300, 3000, 10,000 and 20,000.
  • the scales indicated on each photograph make it possible to measure the sizes of observable details.
  • the dark parts correspond to the porosity while the pale portions correspond to the catalytic substance.
  • catalyst A has effectively a structure of the "sea-urchins" type corresponding to a juxtaposition of conglomerates having in majority an average size of 3.5 micrometers, each conglomerate being formed of elongate acicular plates, generally radially assembled with respect to the center of the conglomerates.
  • the sizes of the acicular plates can be measured in particular on FIG.
  • the ratio of the average length to the average width is hence from about 8 to 16 and the ratio of the average length to the average thickness is from about 120 to 480.
  • FIG. 1 shows in particular the aggregate pore distribution curve of catalyst A.
  • the diameter of the pores (D), expressed in nanometers, is plotted in abcissae and the aggregate pore volume (V), expressed in cm 3 /g, in ordinates. It is observed that the distribution conforms with the definition of the invention and particularly that it does not comprise a well apparent intermediate inflexion point.
  • presulfurized catalyst (A) The passage of the charge and hydrogen over presulfurized catalyst (A) is effected in the following conditions:
  • the effluent is fed, with hydrogen, to a reactor comprising two successive catalyst beds:
  • the carrier of this catalyst is alumina of low acidity, having a neutralization heat by NH 3 adsorption of 20 joules/g, a specific surface of 140 m 2 /g and a pore volume of 0.48 cm 3 /g.
  • This catalyst is sold on the trade by Societe Francaise PROCATALYSE under reference LD 145.
  • Its carrier is of the ⁇ alumina type, having a specific surface of 210 m 2 /g, its pore volume being 0.52 cm 3 /g; this carrier has a neutralization heat by NH 3 adsorption of 40 joules/g.
  • the ratio by weight of the catalyst of the second bed to that of the first bed is hence 4.
  • the temperature in the reactor is from 370° to 400° C. and the pressure 140 bars.
  • the hourly feed rate of liquid charge is 0.5 m 3 m 3 /h, the hydrogen proportion with respect to the charge is 1200 Nm 3 /m 3 .
  • the process has thus resulted in the conversion of a heavy viscous, non-transportable crude oil of high impurity content, to a stable, easily transportable, synthetic crude oil of low impurity content.
  • the life time of the catalysts is remarkable in view of the charge.
  • the retention capacity of these catalysts is far above 100 g of metals for 100 g of fresh catalyst; the life time of this catalytic system is in direct relation with the space velocity selected for the treatment.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)
US06/567,208 1982-12-30 1983-12-30 Heavy oil process with hydrovisbreaking, hydrodemetallation and hydrodesulfuration Expired - Lifetime US4510042A (en)

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FR8222210 1982-12-30
FR8222210A FR2538814B1 (fr) 1982-12-30 1982-12-30 Procede de traitement d'une huile lourde ou d'une fraction d'huile lourde pour les convertir en fractions plus legeres

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EP (1) EP0113284B1 (de)
JP (1) JPH0788513B2 (de)
CA (1) CA1226843A (de)
DE (1) DE3375154D1 (de)
FR (1) FR2538814B1 (de)
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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5413702A (en) * 1992-02-21 1995-05-09 Mobil Oil Corporation High severity visbreaking of residual oil
US6132597A (en) * 1997-06-10 2000-10-17 Institut Francais Du Petrole Hydrotreating hydrocarbon feeds in an ebullating bed reactor
WO2002072730A2 (en) * 2001-03-12 2002-09-19 Fina Technology, Inc. Hydrofining process
US20080149531A1 (en) * 2006-12-21 2008-06-26 Magalie Roy-Auberger Process for slurry phase hydroconversion of heavy hydrocarbon feeds and/or coal using a supported catalyst
US20090166260A1 (en) * 2005-12-22 2009-07-02 Stephane Kressmann Irregularly shaped non-spherical supported catalyst, and a process for hydroconverting heavy oil fractions
CN101384364B (zh) * 2005-12-22 2012-03-21 法国石油公司 不规则形状的非球形负载催化剂和重油馏分的加氢转化方法
CN103691488A (zh) * 2013-12-19 2014-04-02 西南石油大学 一种稠油注空气氧化降粘催化剂及其制备方法
US11001770B2 (en) 2017-07-17 2021-05-11 Saudi Arabian Oil Company Systems and methods for processing heavy oils by oil upgrading followed by refining
US11084992B2 (en) * 2016-06-02 2021-08-10 Saudi Arabian Oil Company Systems and methods for upgrading heavy oils
US11795406B2 (en) 2017-02-12 2023-10-24 Magemä Technology LLC Multi-stage device and process for production of a low sulfur heavy marine fuel oil from distressed heavy fuel oil materials
US11884883B2 (en) 2017-02-12 2024-01-30 MagêmãTechnology LLC Multi-stage device and process for production of a low sulfur heavy marine fuel oil
US12025435B2 (en) 2017-02-12 2024-07-02 Magēmã Technology LLC Multi-stage device and process for production of a low sulfur heavy marine fuel oil
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FR3027910B1 (fr) 2014-11-04 2016-12-09 Ifp Energies Now Procede de conversion de charges petrolieres comprenant une etape d'hydrotraitement en lit fixe, une etape d'hydrocraquage en lit bouillonnant, une etape de maturation et une etape de separation des sediments pour la production de fiouls a basse teneur en sediments.
FR3027912B1 (fr) 2014-11-04 2018-04-27 IFP Energies Nouvelles Procede de production de combustibles de type fuel lourd a partir d'une charge hydrocarbonee lourde utilisant une separation entre l'etape d'hydrotraitement et l'etape d'hydrocraquage
FR3027911B1 (fr) 2014-11-04 2018-04-27 IFP Energies Nouvelles Procede de conversion de charges petrolieres comprenant une etape d'hydrocraquage en lit bouillonnant, une etape de maturation et une etape de separation des sediments pour la production de fiouls a basse teneur en sediments
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FR3036704B1 (fr) 2015-06-01 2017-05-26 Ifp Energies Now Procede de conversion de charges comprenant une etape de viscoreduction, une etape de precipitation et une etape de separation des sediments pour la production de fiouls
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FR3129945A1 (fr) 2021-12-03 2023-06-09 IFP Energies Nouvelles Procede de traitement d’huiles de pyrolyse de plastiques incluant une etape d’hydrogenation et une separation a chaud
FR3133618A1 (fr) 2022-03-17 2023-09-22 IFP Energies Nouvelles Hydroconversion en lit bouillonnant ou hybride bouillonnant-entraîné d’une charge comportant une fraction d’huile de pyrolyse de plastiques et/ou de combustibles solides de recuperation
FR3135090A1 (fr) 2022-04-29 2023-11-03 IFP Energies Nouvelles Procede de traitement d’huile de pyrolyse de plastiques incluant une etape de recyclage d’h2s
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FR3144155A1 (fr) 2022-12-21 2024-06-28 IFP Energies Nouvelles Procede de traitement d’huiles de pyrolyse de plastiques et/ou de pneus incluant l’elimination des halogenures avant une etape d’hydrotraitement
FR3144153A1 (fr) 2022-12-21 2024-06-28 IFP Energies Nouvelles Procede de traitement d’huiles de pyrolyse de plastiques et/ou de pneus incluant l’elimination des halogenures par lavage avant une etape d’hydrotraitement

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US5413702A (en) * 1992-02-21 1995-05-09 Mobil Oil Corporation High severity visbreaking of residual oil
US6132597A (en) * 1997-06-10 2000-10-17 Institut Francais Du Petrole Hydrotreating hydrocarbon feeds in an ebullating bed reactor
WO2002072730A2 (en) * 2001-03-12 2002-09-19 Fina Technology, Inc. Hydrofining process
WO2002072730A3 (en) * 2001-03-12 2003-09-18 Fina Technology Hydrofining process
CN101384364B (zh) * 2005-12-22 2012-03-21 法国石油公司 不规则形状的非球形负载催化剂和重油馏分的加氢转化方法
US20090166260A1 (en) * 2005-12-22 2009-07-02 Stephane Kressmann Irregularly shaped non-spherical supported catalyst, and a process for hydroconverting heavy oil fractions
US8618017B2 (en) 2005-12-22 2013-12-31 IFP Energies Nouvelles Irregularly shaped non-spherical supported catalyst, and a process for hydroconversion heavy oil fractions
US20080149531A1 (en) * 2006-12-21 2008-06-26 Magalie Roy-Auberger Process for slurry phase hydroconversion of heavy hydrocarbon feeds and/or coal using a supported catalyst
US7807044B2 (en) 2006-12-21 2010-10-05 IFP Energies Nouvelles Process for slurry phase hydroconversion of heavy hydrocarbon feeds and/or coal using a supported catalyst
CN103691488A (zh) * 2013-12-19 2014-04-02 西南石油大学 一种稠油注空气氧化降粘催化剂及其制备方法
CN103691488B (zh) * 2013-12-19 2015-07-29 西南石油大学 一种稠油注空气氧化降粘催化剂及其制备方法
US11084992B2 (en) * 2016-06-02 2021-08-10 Saudi Arabian Oil Company Systems and methods for upgrading heavy oils
US11795406B2 (en) 2017-02-12 2023-10-24 Magemä Technology LLC Multi-stage device and process for production of a low sulfur heavy marine fuel oil from distressed heavy fuel oil materials
US11884883B2 (en) 2017-02-12 2024-01-30 MagêmãTechnology LLC Multi-stage device and process for production of a low sulfur heavy marine fuel oil
US11912945B2 (en) 2017-02-12 2024-02-27 Magēmā Technology LLC Process and device for treating high sulfur heavy marine fuel oil for use as feedstock in a subsequent refinery unit
US12025435B2 (en) 2017-02-12 2024-07-02 Magēmã Technology LLC Multi-stage device and process for production of a low sulfur heavy marine fuel oil
US12071592B2 (en) 2017-02-12 2024-08-27 Magēmā Technology LLC Multi-stage process and device utilizing structured catalyst beds and reactive distillation for the production of a low sulfur heavy marine fuel oil
US11001770B2 (en) 2017-07-17 2021-05-11 Saudi Arabian Oil Company Systems and methods for processing heavy oils by oil upgrading followed by refining

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FR2538814A1 (fr) 1984-07-06
FR2538814B1 (fr) 1986-06-27
JPS59166590A (ja) 1984-09-19
CA1226843A (fr) 1987-09-15
EP0113284A1 (de) 1984-07-11
ZA848B (en) 1985-08-28
EP0113284B1 (de) 1988-01-07
DE3375154D1 (en) 1988-02-11
JPH0788513B2 (ja) 1995-09-27
MX172212B (es) 1993-12-07

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